CN104918985A - Method for manufacturing sulfone polymer membrane - Google Patents
Method for manufacturing sulfone polymer membrane Download PDFInfo
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- CN104918985A CN104918985A CN201380071063.XA CN201380071063A CN104918985A CN 104918985 A CN104918985 A CN 104918985A CN 201380071063 A CN201380071063 A CN 201380071063A CN 104918985 A CN104918985 A CN 104918985A
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- 238000000034 method Methods 0.000 title claims abstract description 47
- 150000003457 sulfones Chemical class 0.000 title claims abstract description 18
- 238000004519 manufacturing process Methods 0.000 title claims abstract description 13
- 229920005597 polymer membrane Polymers 0.000 title abstract 2
- 239000000203 mixture Substances 0.000 claims abstract description 115
- 239000002904 solvent Substances 0.000 claims abstract description 89
- IAZDPXIOMUYVGZ-UHFFFAOYSA-N Dimethylsulphoxide Chemical compound CS(C)=O IAZDPXIOMUYVGZ-UHFFFAOYSA-N 0.000 claims abstract description 85
- 229920000642 polymer Polymers 0.000 claims abstract description 47
- 150000005690 diesters Chemical class 0.000 claims abstract description 40
- OAKJQQAXSVQMHS-UHFFFAOYSA-N Hydrazine Chemical compound NN OAKJQQAXSVQMHS-UHFFFAOYSA-N 0.000 claims abstract description 22
- 125000005842 heteroatom Chemical group 0.000 claims abstract description 13
- 125000004433 nitrogen atom Chemical group N* 0.000 claims abstract description 13
- 239000011877 solvent mixture Substances 0.000 claims abstract description 10
- 239000001257 hydrogen Substances 0.000 claims abstract description 3
- 229910052739 hydrogen Inorganic materials 0.000 claims abstract description 3
- 125000004435 hydrogen atom Chemical class [H]* 0.000 claims abstract description 3
- 125000002947 alkylene group Chemical group 0.000 claims abstract 2
- 239000000126 substance Substances 0.000 claims description 47
- -1 alkaline earth metal sulfonate Chemical class 0.000 claims description 41
- 229920000036 polyvinylpyrrolidone Polymers 0.000 claims description 13
- 239000001267 polyvinylpyrrolidone Substances 0.000 claims description 12
- 235000013855 polyvinylpyrrolidone Nutrition 0.000 claims description 12
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 11
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 claims description 10
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 claims description 9
- 125000000217 alkyl group Chemical group 0.000 claims description 9
- 150000002148 esters Chemical class 0.000 claims description 9
- 229910052799 carbon Inorganic materials 0.000 claims description 8
- 238000007766 curtain coating Methods 0.000 claims description 8
- 239000011148 porous material Substances 0.000 claims description 8
- 238000002360 preparation method Methods 0.000 claims description 8
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 7
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 claims description 7
- 125000004432 carbon atom Chemical group C* 0.000 claims description 7
- 150000002191 fatty alcohols Chemical class 0.000 claims description 7
- 239000012530 fluid Substances 0.000 claims description 7
- 239000000463 material Substances 0.000 claims description 7
- 125000003118 aryl group Chemical group 0.000 claims description 6
- 125000003710 aryl alkyl group Chemical group 0.000 claims description 5
- 229910052784 alkaline earth metal Inorganic materials 0.000 claims description 4
- 229910052728 basic metal Inorganic materials 0.000 claims description 4
- 150000003818 basic metals Chemical class 0.000 claims description 4
- 229920006254 polymer film Polymers 0.000 claims description 4
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 claims description 2
- 229920003171 Poly (ethylene oxide) Polymers 0.000 claims description 2
- 125000000304 alkynyl group Chemical group 0.000 claims description 2
- 150000001408 amides Chemical class 0.000 claims description 2
- 150000001412 amines Chemical group 0.000 claims description 2
- 150000001732 carboxylic acid derivatives Chemical class 0.000 claims description 2
- 229910052736 halogen Inorganic materials 0.000 claims description 2
- 150000002367 halogens Chemical class 0.000 claims description 2
- WGCNASOHLSPBMP-UHFFFAOYSA-N hydroxyacetaldehyde Natural products OCC=O WGCNASOHLSPBMP-UHFFFAOYSA-N 0.000 claims description 2
- 150000003949 imides Chemical class 0.000 claims description 2
- 125000001453 quaternary ammonium group Chemical group 0.000 claims description 2
- 125000002769 thiazolinyl group Chemical group 0.000 claims description 2
- 150000003568 thioethers Chemical class 0.000 claims description 2
- 229910052757 nitrogen Inorganic materials 0.000 abstract description 2
- 125000004122 cyclic group Chemical group 0.000 abstract 2
- 125000001183 hydrocarbyl group Chemical group 0.000 abstract 1
- MTHSVFCYNBDYFN-UHFFFAOYSA-N diethylene glycol Chemical compound OCCOCCO MTHSVFCYNBDYFN-UHFFFAOYSA-N 0.000 description 25
- 239000012528 membrane Substances 0.000 description 14
- 229920006393 polyether sulfone Polymers 0.000 description 14
- 239000004695 Polyether sulfone Substances 0.000 description 13
- 239000000835 fiber Substances 0.000 description 12
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 description 9
- SECXISVLQFMRJM-UHFFFAOYSA-N N-Methylpyrrolidone Chemical compound CN1CCCC1=O SECXISVLQFMRJM-UHFFFAOYSA-N 0.000 description 8
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 8
- 238000002156 mixing Methods 0.000 description 8
- 238000005516 engineering process Methods 0.000 description 7
- 229920002492 poly(sulfone) Polymers 0.000 description 7
- 238000001556 precipitation Methods 0.000 description 7
- IBMRTYCHDPMBFN-UHFFFAOYSA-N Mono-Me ester-Pentanedioic acid Natural products COC(=O)CCCC(O)=O IBMRTYCHDPMBFN-UHFFFAOYSA-N 0.000 description 6
- FXHOOIRPVKKKFG-UHFFFAOYSA-N N,N-Dimethylacetamide Chemical compound CN(C)C(C)=O FXHOOIRPVKKKFG-UHFFFAOYSA-N 0.000 description 6
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 description 6
- 210000001601 blood-air barrier Anatomy 0.000 description 5
- 238000005266 casting Methods 0.000 description 5
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 description 5
- 150000002430 hydrocarbons Chemical group 0.000 description 5
- 239000007788 liquid Substances 0.000 description 5
- 229920012287 polyphenylene sulfone Polymers 0.000 description 5
- 230000008569 process Effects 0.000 description 5
- OVSKIKFHRZPJSS-UHFFFAOYSA-N 2,4-D Chemical compound OC(=O)COC1=CC=C(Cl)C=C1Cl OVSKIKFHRZPJSS-UHFFFAOYSA-N 0.000 description 4
- PAYRUJLWNCNPSJ-UHFFFAOYSA-N Aniline Chemical compound NC1=CC=CC=C1 PAYRUJLWNCNPSJ-UHFFFAOYSA-N 0.000 description 4
- JUJWROOIHBZHMG-UHFFFAOYSA-N Pyridine Chemical compound C1=CC=NC=C1 JUJWROOIHBZHMG-UHFFFAOYSA-N 0.000 description 4
- 238000005345 coagulation Methods 0.000 description 4
- 230000015271 coagulation Effects 0.000 description 4
- XLLIQLLCWZCATF-UHFFFAOYSA-N ethylene glycol monomethyl ether acetate Natural products COCCOC(C)=O XLLIQLLCWZCATF-UHFFFAOYSA-N 0.000 description 4
- 239000012071 phase Substances 0.000 description 4
- PBKONEOXTCPAFI-UHFFFAOYSA-N 1,2,4-trichlorobenzene Chemical compound ClC1=CC=C(Cl)C(Cl)=C1 PBKONEOXTCPAFI-UHFFFAOYSA-N 0.000 description 3
- RFFLAFLAYFXFSW-UHFFFAOYSA-N 1,2-dichlorobenzene Chemical compound ClC1=CC=CC=C1Cl RFFLAFLAYFXFSW-UHFFFAOYSA-N 0.000 description 3
- ZWEHNKRNPOVVGH-UHFFFAOYSA-N 2-Butanone Chemical compound CCC(C)=O ZWEHNKRNPOVVGH-UHFFFAOYSA-N 0.000 description 3
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 3
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 description 3
- YFBZUWUJSCLVST-UHFFFAOYSA-N CC(C)(c1ccccc11)OC1=O Chemical compound CC(C)(c1ccccc11)OC1=O YFBZUWUJSCLVST-UHFFFAOYSA-N 0.000 description 3
- MUXOBHXGJLMRAB-UHFFFAOYSA-N Dimethyl succinate Chemical compound COC(=O)CCC(=O)OC MUXOBHXGJLMRAB-UHFFFAOYSA-N 0.000 description 3
- SNRUBQQJIBEYMU-UHFFFAOYSA-N Dodecane Natural products CCCCCCCCCCCC SNRUBQQJIBEYMU-UHFFFAOYSA-N 0.000 description 3
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 3
- 239000012298 atmosphere Substances 0.000 description 3
- MVPPADPHJFYWMZ-UHFFFAOYSA-N chlorobenzene Chemical compound ClC1=CC=CC=C1 MVPPADPHJFYWMZ-UHFFFAOYSA-N 0.000 description 3
- 230000006378 damage Effects 0.000 description 3
- 238000009826 distribution Methods 0.000 description 3
- 231100000025 genetic toxicology Toxicity 0.000 description 3
- 230000001738 genotoxic effect Effects 0.000 description 3
- YCOZIPAWZNQLMR-UHFFFAOYSA-N heptane - octane Natural products CCCCCCCCCCCCCCC YCOZIPAWZNQLMR-UHFFFAOYSA-N 0.000 description 3
- 229930195733 hydrocarbon Natural products 0.000 description 3
- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical compound CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 description 3
- 125000003367 polycyclic group Chemical group 0.000 description 3
- 239000002243 precursor Substances 0.000 description 3
- 238000003756 stirring Methods 0.000 description 3
- 238000003860 storage Methods 0.000 description 3
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 description 3
- RSJKGSCJYJTIGS-UHFFFAOYSA-N undecane Chemical compound CCCCCCCCCCC RSJKGSCJYJTIGS-UHFFFAOYSA-N 0.000 description 3
- YEJRWHAVMIAJKC-UHFFFAOYSA-N 4-Butyrolactone Chemical compound O=C1CCCO1 YEJRWHAVMIAJKC-UHFFFAOYSA-N 0.000 description 2
- HEDRZPFGACZZDS-UHFFFAOYSA-N Chloroform Chemical compound ClC(Cl)Cl HEDRZPFGACZZDS-UHFFFAOYSA-N 0.000 description 2
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 description 2
- UDSFAEKRVUSQDD-UHFFFAOYSA-N Dimethyl adipate Chemical compound COC(=O)CCCCC(=O)OC UDSFAEKRVUSQDD-UHFFFAOYSA-N 0.000 description 2
- NIQCNGHVCWTJSM-UHFFFAOYSA-N Dimethyl phthalate Chemical compound COC(=O)C1=CC=CC=C1C(=O)OC NIQCNGHVCWTJSM-UHFFFAOYSA-N 0.000 description 2
- NTIZESTWPVYFNL-UHFFFAOYSA-N Methyl isobutyl ketone Chemical compound CC(C)CC(C)=O NTIZESTWPVYFNL-UHFFFAOYSA-N 0.000 description 2
- UIHCLUNTQKBZGK-UHFFFAOYSA-N Methyl isobutyl ketone Natural products CCC(C)C(C)=O UIHCLUNTQKBZGK-UHFFFAOYSA-N 0.000 description 2
- IMNFDUFMRHMDMM-UHFFFAOYSA-N N-Heptane Chemical compound CCCCCCC IMNFDUFMRHMDMM-UHFFFAOYSA-N 0.000 description 2
- UFWIBTONFRDIAS-UHFFFAOYSA-N Naphthalene Chemical compound C1=CC=CC2=CC=CC=C21 UFWIBTONFRDIAS-UHFFFAOYSA-N 0.000 description 2
- CTQNGGLPUBDAKN-UHFFFAOYSA-N O-Xylene Chemical compound CC1=CC=CC=C1C CTQNGGLPUBDAKN-UHFFFAOYSA-N 0.000 description 2
- MHABMANUFPZXEB-UHFFFAOYSA-N O-demethyl-aloesaponarin I Natural products O=C1C2=CC=CC(O)=C2C(=O)C2=C1C=C(O)C(C(O)=O)=C2C MHABMANUFPZXEB-UHFFFAOYSA-N 0.000 description 2
- OFBQJSOFQDEBGM-UHFFFAOYSA-N Pentane Chemical compound CCCCC OFBQJSOFQDEBGM-UHFFFAOYSA-N 0.000 description 2
- 229920012266 Poly(ether sulfone) PES Polymers 0.000 description 2
- 125000001118 alkylidene group Chemical group 0.000 description 2
- 230000003321 amplification Effects 0.000 description 2
- 150000004945 aromatic hydrocarbons Chemical class 0.000 description 2
- 230000008901 benefit Effects 0.000 description 2
- 125000001797 benzyl group Chemical group [H]C1=C([H])C([H])=C(C([H])=C1[H])C([H])([H])* 0.000 description 2
- DKPFZGUDAPQIHT-UHFFFAOYSA-N butyl acetate Chemical compound CCCCOC(C)=O DKPFZGUDAPQIHT-UHFFFAOYSA-N 0.000 description 2
- 125000000484 butyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 2
- 230000008859 change Effects 0.000 description 2
- RWGFKTVRMDUZSP-UHFFFAOYSA-N cumene Chemical compound CC(C)C1=CC=CC=C1 RWGFKTVRMDUZSP-UHFFFAOYSA-N 0.000 description 2
- 125000000113 cyclohexyl group Chemical group [H]C1([H])C([H])([H])C([H])([H])C([H])(*)C([H])([H])C1([H])[H] 0.000 description 2
- DIOQZVSQGTUSAI-UHFFFAOYSA-N decane Chemical compound CCCCCCCCCC DIOQZVSQGTUSAI-UHFFFAOYSA-N 0.000 description 2
- SWXVUIWOUIDPGS-UHFFFAOYSA-N diacetone alcohol Chemical compound CC(=O)CC(C)(C)O SWXVUIWOUIDPGS-UHFFFAOYSA-N 0.000 description 2
- RZZLQHQXWZLBCJ-UHFFFAOYSA-N dimethyl 2-ethylbutanedioate Chemical compound COC(=O)C(CC)CC(=O)OC RZZLQHQXWZLBCJ-UHFFFAOYSA-N 0.000 description 2
- ZWKKRUNHAVNSFW-UHFFFAOYSA-N dimethyl 2-methylpentanedioate Chemical compound COC(=O)CCC(C)C(=O)OC ZWKKRUNHAVNSFW-UHFFFAOYSA-N 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 239000007789 gas Substances 0.000 description 2
- 239000012535 impurity Substances 0.000 description 2
- 125000001972 isopentyl group Chemical group [H]C([H])([H])C([H])(C([H])([H])[H])C([H])([H])C([H])([H])* 0.000 description 2
- HJOVHMDZYOCNQW-UHFFFAOYSA-N isophorone Chemical compound CC1=CC(=O)CC(C)(C)C1 HJOVHMDZYOCNQW-UHFFFAOYSA-N 0.000 description 2
- 229940043265 methyl isobutyl ketone Drugs 0.000 description 2
- 125000000740 n-pentyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 description 2
- 125000004123 n-propyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])* 0.000 description 2
- BKIMMITUMNQMOS-UHFFFAOYSA-N nonane Chemical compound CCCCCCCCC BKIMMITUMNQMOS-UHFFFAOYSA-N 0.000 description 2
- 238000003199 nucleic acid amplification method Methods 0.000 description 2
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 description 2
- 239000002244 precipitate Substances 0.000 description 2
- UMJSCPRVCHMLSP-UHFFFAOYSA-N pyridine Natural products COC1=CC=CN=C1 UMJSCPRVCHMLSP-UHFFFAOYSA-N 0.000 description 2
- 229930195734 saturated hydrocarbon Natural products 0.000 description 2
- 238000000926 separation method Methods 0.000 description 2
- 238000009987 spinning Methods 0.000 description 2
- BGHCVCJVXZWKCC-UHFFFAOYSA-N tetradecane Chemical compound CCCCCCCCCCCCCC BGHCVCJVXZWKCC-UHFFFAOYSA-N 0.000 description 2
- IIYFAKIEWZDVMP-UHFFFAOYSA-N tridecane Chemical compound CCCCCCCCCCCCC IIYFAKIEWZDVMP-UHFFFAOYSA-N 0.000 description 2
- UOCLXMDMGBRAIB-UHFFFAOYSA-N 1,1,1-trichloroethane Chemical compound CC(Cl)(Cl)Cl UOCLXMDMGBRAIB-UHFFFAOYSA-N 0.000 description 1
- UBOXGVDOUJQMTN-UHFFFAOYSA-N 1,1,2-trichloroethane Chemical compound ClCC(Cl)Cl UBOXGVDOUJQMTN-UHFFFAOYSA-N 0.000 description 1
- UWHSPZZUAYSGTB-UHFFFAOYSA-N 1,1,3,3-tetraethylurea Chemical compound CCN(CC)C(=O)N(CC)CC UWHSPZZUAYSGTB-UHFFFAOYSA-N 0.000 description 1
- AVQQQNCBBIEMEU-UHFFFAOYSA-N 1,1,3,3-tetramethylurea Chemical compound CN(C)C(=O)N(C)C AVQQQNCBBIEMEU-UHFFFAOYSA-N 0.000 description 1
- WSLDOOZREJYCGB-UHFFFAOYSA-N 1,2-Dichloroethane Chemical compound ClCCCl WSLDOOZREJYCGB-UHFFFAOYSA-N 0.000 description 1
- PQBOTZNYFQWRHU-UHFFFAOYSA-N 1,2-dichlorobutane Chemical compound CCC(Cl)CCl PQBOTZNYFQWRHU-UHFFFAOYSA-N 0.000 description 1
- LZDKZFUFMNSQCJ-UHFFFAOYSA-N 1,2-diethoxyethane Chemical compound CCOCCOCC LZDKZFUFMNSQCJ-UHFFFAOYSA-N 0.000 description 1
- ZPQOPVIELGIULI-UHFFFAOYSA-N 1,3-dichlorobenzene Chemical compound ClC1=CC=CC(Cl)=C1 ZPQOPVIELGIULI-UHFFFAOYSA-N 0.000 description 1
- VAYTZRYEBVHVLE-UHFFFAOYSA-N 1,3-dioxol-2-one Chemical compound O=C1OC=CO1 VAYTZRYEBVHVLE-UHFFFAOYSA-N 0.000 description 1
- RYHBNJHYFVUHQT-UHFFFAOYSA-N 1,4-Dioxane Chemical compound C1COCCO1 RYHBNJHYFVUHQT-UHFFFAOYSA-N 0.000 description 1
- GDXHBFHOEYVPED-UHFFFAOYSA-N 1-(2-butoxyethoxy)butane Chemical compound CCCCOCCOCCCC GDXHBFHOEYVPED-UHFFFAOYSA-N 0.000 description 1
- VFWCMGCRMGJXDK-UHFFFAOYSA-N 1-chlorobutane Chemical compound CCCCCl VFWCMGCRMGJXDK-UHFFFAOYSA-N 0.000 description 1
- 125000006219 1-ethylpentyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])(*)C([H])([H])C([H])([H])[H] 0.000 description 1
- OAYXUHPQHDHDDZ-UHFFFAOYSA-N 2-(2-butoxyethoxy)ethanol Chemical compound CCCCOCCOCCO OAYXUHPQHDHDDZ-UHFFFAOYSA-N 0.000 description 1
- SBASXUCJHJRPEV-UHFFFAOYSA-N 2-(2-methoxyethoxy)ethanol Chemical compound COCCOCCO SBASXUCJHJRPEV-UHFFFAOYSA-N 0.000 description 1
- XNWFRZJHXBZDAG-UHFFFAOYSA-N 2-METHOXYETHANOL Chemical compound COCCO XNWFRZJHXBZDAG-UHFFFAOYSA-N 0.000 description 1
- PTTPXKJBFFKCEK-UHFFFAOYSA-N 2-Methyl-4-heptanone Chemical compound CC(C)CC(=O)CC(C)C PTTPXKJBFFKCEK-UHFFFAOYSA-N 0.000 description 1
- POAOYUHQDCAZBD-UHFFFAOYSA-N 2-butoxyethanol Chemical compound CCCCOCCO POAOYUHQDCAZBD-UHFFFAOYSA-N 0.000 description 1
- ZNQVEEAIQZEUHB-UHFFFAOYSA-N 2-ethoxyethanol Chemical compound CCOCCO ZNQVEEAIQZEUHB-UHFFFAOYSA-N 0.000 description 1
- SVONRAPFKPVNKG-UHFFFAOYSA-N 2-ethoxyethyl acetate Chemical compound CCOCCOC(C)=O SVONRAPFKPVNKG-UHFFFAOYSA-N 0.000 description 1
- 125000006176 2-ethylbutyl group Chemical group [H]C([H])([H])C([H])([H])C([H])(C([H])([H])*)C([H])([H])C([H])([H])[H] 0.000 description 1
- QCDWFXQBSFUVSP-UHFFFAOYSA-N 2-phenoxyethanol Chemical compound OCCOC1=CC=CC=C1 QCDWFXQBSFUVSP-UHFFFAOYSA-N 0.000 description 1
- CUZKCNWZBXLAJX-UHFFFAOYSA-N 2-phenylmethoxyethanol Chemical compound OCCOCC1=CC=CC=C1 CUZKCNWZBXLAJX-UHFFFAOYSA-N 0.000 description 1
- YEYKMVJDLWJFOA-UHFFFAOYSA-N 2-propoxyethanol Chemical compound CCCOCCO YEYKMVJDLWJFOA-UHFFFAOYSA-N 0.000 description 1
- 125000004337 3-ethylpentyl group Chemical group [H]C([H])([H])C([H])([H])C([H])(C([H])([H])C([H])([H])[H])C([H])([H])C([H])([H])* 0.000 description 1
- 125000003469 3-methylhexyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])(C([H])([H])[H])C([H])([H])C([H])([H])* 0.000 description 1
- RZVAJINKPMORJF-UHFFFAOYSA-N Acetaminophen Chemical compound CC(=O)NC1=CC=C(O)C=C1 RZVAJINKPMORJF-UHFFFAOYSA-N 0.000 description 1
- 0 C*C(C([C@@](C=C1)*(C)=CO)C=C1[Al]c1ccc(C(O)=O)c(C(*c(cc2)ccc2S(c2ccc(C)cc2)(=O)=O)=O)c1)=O Chemical compound C*C(C([C@@](C=C1)*(C)=CO)C=C1[Al]c1ccc(C(O)=O)c(C(*c(cc2)ccc2S(c2ccc(C)cc2)(=O)=O)=O)c1)=O 0.000 description 1
- GAWIXWVDTYZWAW-UHFFFAOYSA-N C[CH]O Chemical group C[CH]O GAWIXWVDTYZWAW-UHFFFAOYSA-N 0.000 description 1
- 239000004215 Carbon black (E152) Substances 0.000 description 1
- OZNFRTCNYSEMDH-UHFFFAOYSA-N Cc(cc1)ccc1S(c(cc1)ccc1N(C(c(c1c2)ccc2[Al](C)c(cc2)cc(C(NC)=O)c2C(O)=O)=O)C1=O)(=O)=O Chemical compound Cc(cc1)ccc1S(c(cc1)ccc1N(C(c(c1c2)ccc2[Al](C)c(cc2)cc(C(NC)=O)c2C(O)=O)=O)C1=O)(=O)=O OZNFRTCNYSEMDH-UHFFFAOYSA-N 0.000 description 1
- FGWHXVKRBGANBK-UHFFFAOYSA-N Cc(cc1)ccc1S(c(cc1)ccc1N(C(c(c1c2)ccc2[Al](c(cc2)cc(C(N3C)=O)c2C3=O)=C)=O)C1=O)(=O)=O Chemical compound Cc(cc1)ccc1S(c(cc1)ccc1N(C(c(c1c2)ccc2[Al](c(cc2)cc(C(N3C)=O)c2C3=O)=C)=O)C1=O)(=O)=O FGWHXVKRBGANBK-UHFFFAOYSA-N 0.000 description 1
- XDTMQSROBMDMFD-UHFFFAOYSA-N Cyclohexane Chemical compound C1CCCCC1 XDTMQSROBMDMFD-UHFFFAOYSA-N 0.000 description 1
- OIFBSDVPJOWBCH-UHFFFAOYSA-N Diethyl carbonate Chemical compound CCOC(=O)OCC OIFBSDVPJOWBCH-UHFFFAOYSA-N 0.000 description 1
- DKMROQRQHGEIOW-UHFFFAOYSA-N Diethyl succinate Chemical compound CCOC(=O)CCC(=O)OCC DKMROQRQHGEIOW-UHFFFAOYSA-N 0.000 description 1
- RDOFJDLLWVCMRU-UHFFFAOYSA-N Diisobutyl adipate Chemical compound CC(C)COC(=O)CCCCC(=O)OCC(C)C RDOFJDLLWVCMRU-UHFFFAOYSA-N 0.000 description 1
- ZAFNJMIOTHYJRJ-UHFFFAOYSA-N Diisopropyl ether Chemical compound CC(C)OC(C)C ZAFNJMIOTHYJRJ-UHFFFAOYSA-N 0.000 description 1
- XTHFKEDIFFGKHM-UHFFFAOYSA-N Dimethoxyethane Chemical compound COCCOC XTHFKEDIFFGKHM-UHFFFAOYSA-N 0.000 description 1
- KMTRUDSVKNLOMY-UHFFFAOYSA-N Ethylene carbonate Chemical compound O=C1OCCO1 KMTRUDSVKNLOMY-UHFFFAOYSA-N 0.000 description 1
- 206010015946 Eye irritation Diseases 0.000 description 1
- 206010065042 Immune reconstitution inflammatory syndrome Diseases 0.000 description 1
- BZLVMXJERCGZMT-UHFFFAOYSA-N Methyl tert-butyl ether Chemical compound COC(C)(C)C BZLVMXJERCGZMT-UHFFFAOYSA-N 0.000 description 1
- WRQNANDWMGAFTP-UHFFFAOYSA-N Methylacetoacetic acid Chemical compound COC(=O)CC(C)=O WRQNANDWMGAFTP-UHFFFAOYSA-N 0.000 description 1
- SUAKHGWARZSWIH-UHFFFAOYSA-N N,N‐diethylformamide Chemical compound CCN(CC)C=O SUAKHGWARZSWIH-UHFFFAOYSA-N 0.000 description 1
- 101100208039 Rattus norvegicus Trpv5 gene Proteins 0.000 description 1
- 206010040880 Skin irritation Diseases 0.000 description 1
- XSTXAVWGXDQKEL-UHFFFAOYSA-N Trichloroethylene Chemical compound ClC=C(Cl)Cl XSTXAVWGXDQKEL-UHFFFAOYSA-N 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 238000005054 agglomeration Methods 0.000 description 1
- 230000002776 aggregation Effects 0.000 description 1
- 125000002723 alicyclic group Chemical group 0.000 description 1
- 125000001931 aliphatic group Chemical group 0.000 description 1
- 150000001338 aliphatic hydrocarbons Chemical class 0.000 description 1
- 150000004996 alkyl benzenes Chemical class 0.000 description 1
- 125000003368 amide group Chemical group 0.000 description 1
- 150000008378 aryl ethers Chemical class 0.000 description 1
- BDZGWEUSDXLORW-UHFFFAOYSA-N benzenesulfinylsulfinylbenzene Chemical compound C=1C=CC=CC=1S(=O)S(=O)C1=CC=CC=C1 BDZGWEUSDXLORW-UHFFFAOYSA-N 0.000 description 1
- 125000002619 bicyclic group Chemical group 0.000 description 1
- QCOAPBRVQHMEPF-UHFFFAOYSA-N bis(2-methylpropyl) butanedioate Chemical compound CC(C)COC(=O)CCC(=O)OCC(C)C QCOAPBRVQHMEPF-UHFFFAOYSA-N 0.000 description 1
- UFWRCRCDRAUAAO-UHFFFAOYSA-N bis(2-methylpropyl) pentanedioate Chemical compound CC(C)COC(=O)CCCC(=O)OCC(C)C UFWRCRCDRAUAAO-UHFFFAOYSA-N 0.000 description 1
- 230000000711 cancerogenic effect Effects 0.000 description 1
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 description 1
- 231100000315 carcinogenic Toxicity 0.000 description 1
- 239000013626 chemical specie Substances 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- 239000011248 coating agent Substances 0.000 description 1
- 238000000576 coating method Methods 0.000 description 1
- 238000010276 construction Methods 0.000 description 1
- 238000004320 controlled atmosphere Methods 0.000 description 1
- 238000002425 crystallisation Methods 0.000 description 1
- 230000008025 crystallization Effects 0.000 description 1
- JHIVVAPYMSGYDF-UHFFFAOYSA-N cyclohexanone Chemical compound O=C1CCCCC1 JHIVVAPYMSGYDF-UHFFFAOYSA-N 0.000 description 1
- 125000001511 cyclopentyl group Chemical group [H]C1([H])C([H])([H])C([H])([H])C([H])(*)C1([H])[H] 0.000 description 1
- 125000002704 decyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- QLVWOKQMDLQXNN-UHFFFAOYSA-N dibutyl carbonate Chemical compound CCCCOC(=O)OCCCC QLVWOKQMDLQXNN-UHFFFAOYSA-N 0.000 description 1
- JGFBRKRYDCGYKD-UHFFFAOYSA-N dibutyl(oxo)tin Chemical compound CCCC[Sn](=O)CCCC JGFBRKRYDCGYKD-UHFFFAOYSA-N 0.000 description 1
- 229940117389 dichlorobenzene Drugs 0.000 description 1
- OUWSNHWQZPEFEX-UHFFFAOYSA-N diethyl glutarate Chemical compound CCOC(=O)CCCC(=O)OCC OUWSNHWQZPEFEX-UHFFFAOYSA-N 0.000 description 1
- XXJWXESWEXIICW-UHFFFAOYSA-N diethylene glycol monoethyl ether Chemical compound CCOCCOCCO XXJWXESWEXIICW-UHFFFAOYSA-N 0.000 description 1
- 229940075557 diethylene glycol monoethyl ether Drugs 0.000 description 1
- 238000009792 diffusion process Methods 0.000 description 1
- 229940031769 diisobutyl adipate Drugs 0.000 description 1
- FBSAITBEAPNWJG-UHFFFAOYSA-N dimethyl phthalate Natural products CC(=O)OC1=CC=CC=C1OC(C)=O FBSAITBEAPNWJG-UHFFFAOYSA-N 0.000 description 1
- 229960001826 dimethylphthalate Drugs 0.000 description 1
- KZTYYGOKRVBIMI-UHFFFAOYSA-N diphenyl sulfone Chemical group C=1C=CC=CC=1S(=O)(=O)C1=CC=CC=C1 KZTYYGOKRVBIMI-UHFFFAOYSA-N 0.000 description 1
- VUPKGFBOKBGHFZ-UHFFFAOYSA-N dipropyl carbonate Chemical compound CCCOC(=O)OCCC VUPKGFBOKBGHFZ-UHFFFAOYSA-N 0.000 description 1
- 238000004090 dissolution Methods 0.000 description 1
- 125000003438 dodecyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 description 1
- 238000001035 drying Methods 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- XHEDLZYGAQSNTR-UHFFFAOYSA-N ethene;hexanedioic acid Chemical compound C=C.C=C.OC(=O)CCCCC(O)=O XHEDLZYGAQSNTR-UHFFFAOYSA-N 0.000 description 1
- JBTWLSYIZRCDFO-UHFFFAOYSA-N ethyl methyl carbonate Chemical compound CCOC(=O)OC JBTWLSYIZRCDFO-UHFFFAOYSA-N 0.000 description 1
- 229940093476 ethylene glycol Drugs 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 231100000013 eye irritation Toxicity 0.000 description 1
- 239000004744 fabric Substances 0.000 description 1
- 230000002349 favourable effect Effects 0.000 description 1
- 239000011888 foil Substances 0.000 description 1
- 230000009477 glass transition Effects 0.000 description 1
- 239000000383 hazardous chemical Substances 0.000 description 1
- VHHHONWQHHHLTI-UHFFFAOYSA-N hexachloroethane Chemical compound ClC(Cl)(Cl)C(Cl)(Cl)Cl VHHHONWQHHHLTI-UHFFFAOYSA-N 0.000 description 1
- 125000004051 hexyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 description 1
- 239000012510 hollow fiber Substances 0.000 description 1
- 239000012456 homogeneous solution Substances 0.000 description 1
- 230000006872 improvement Effects 0.000 description 1
- 230000008595 infiltration Effects 0.000 description 1
- 238000001764 infiltration Methods 0.000 description 1
- 238000011835 investigation Methods 0.000 description 1
- 125000004491 isohexyl group Chemical group C(CCC(C)C)* 0.000 description 1
- JMMWKPVZQRWMSS-UHFFFAOYSA-N isopropanol acetate Natural products CC(C)OC(C)=O JMMWKPVZQRWMSS-UHFFFAOYSA-N 0.000 description 1
- 229940011051 isopropyl acetate Drugs 0.000 description 1
- GWYFCOCPABKNJV-UHFFFAOYSA-N isovaleric acid Chemical compound CC(C)CC(O)=O GWYFCOCPABKNJV-UHFFFAOYSA-N 0.000 description 1
- 239000007791 liquid phase Substances 0.000 description 1
- 239000011159 matrix material Substances 0.000 description 1
- CXHHBNMLPJOKQD-UHFFFAOYSA-M methyl carbonate Chemical compound COC([O-])=O CXHHBNMLPJOKQD-UHFFFAOYSA-M 0.000 description 1
- 238000001000 micrograph Methods 0.000 description 1
- 231100000350 mutagenesis Toxicity 0.000 description 1
- 238000002703 mutagenesis Methods 0.000 description 1
- AJFDBNQQDYLMJN-UHFFFAOYSA-N n,n-diethylacetamide Chemical compound CCN(CC)C(C)=O AJFDBNQQDYLMJN-UHFFFAOYSA-N 0.000 description 1
- 125000001280 n-hexyl group Chemical group C(CCCCC)* 0.000 description 1
- 125000001624 naphthyl group Chemical group 0.000 description 1
- 239000012299 nitrogen atmosphere Substances 0.000 description 1
- TVMXDCGIABBOFY-UHFFFAOYSA-N octane Chemical compound CCCCCCCC TVMXDCGIABBOFY-UHFFFAOYSA-N 0.000 description 1
- 239000003960 organic solvent Substances 0.000 description 1
- 230000003647 oxidation Effects 0.000 description 1
- 238000007254 oxidation reaction Methods 0.000 description 1
- 239000012188 paraffin wax Substances 0.000 description 1
- BNIXVQGCZULYKV-UHFFFAOYSA-N pentachloroethane Chemical compound ClC(Cl)C(Cl)(Cl)Cl BNIXVQGCZULYKV-UHFFFAOYSA-N 0.000 description 1
- 239000003208 petroleum Substances 0.000 description 1
- 229960005323 phenoxyethanol Drugs 0.000 description 1
- 239000002798 polar solvent Substances 0.000 description 1
- 229920005649 polyetherethersulfone Polymers 0.000 description 1
- 230000003389 potentiating effect Effects 0.000 description 1
- 239000000047 product Substances 0.000 description 1
- 101150025733 pub2 gene Proteins 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 231100001260 reprotoxic Toxicity 0.000 description 1
- 125000002914 sec-butyl group Chemical group [H]C([H])([H])C([H])([H])C([H])(*)C([H])([H])[H] 0.000 description 1
- 230000036556 skin irritation Effects 0.000 description 1
- 231100000475 skin irritation Toxicity 0.000 description 1
- 229920001169 thermoplastic Polymers 0.000 description 1
- 239000004416 thermosoftening plastic Substances 0.000 description 1
- 231100000331 toxic Toxicity 0.000 description 1
- 231100000167 toxic agent Toxicity 0.000 description 1
- 230000002588 toxic effect Effects 0.000 description 1
- 239000003440 toxic substance Substances 0.000 description 1
- 231100000419 toxicity Toxicity 0.000 description 1
- 230000001988 toxicity Effects 0.000 description 1
- 230000007704 transition Effects 0.000 description 1
- 230000017105 transposition Effects 0.000 description 1
- DQWPFSLDHJDLRL-UHFFFAOYSA-N triethyl phosphate Chemical compound CCOP(=O)(OCC)OCC DQWPFSLDHJDLRL-UHFFFAOYSA-N 0.000 description 1
- CYTQBVOFDCPGCX-UHFFFAOYSA-N trimethyl phosphite Chemical compound COP(OC)OC CYTQBVOFDCPGCX-UHFFFAOYSA-N 0.000 description 1
- 238000002166 wet spinning Methods 0.000 description 1
Classifications
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D67/00—Processes specially adapted for manufacturing semi-permeable membranes for separation processes or apparatus
- B01D67/0002—Organic membrane manufacture
- B01D67/0009—Organic membrane manufacture by phase separation, sol-gel transition, evaporation or solvent quenching
- B01D67/0011—Casting solutions therefor
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D67/00—Processes specially adapted for manufacturing semi-permeable membranes for separation processes or apparatus
- B01D67/0002—Organic membrane manufacture
- B01D67/0009—Organic membrane manufacture by phase separation, sol-gel transition, evaporation or solvent quenching
- B01D67/0013—Casting processes
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D69/00—Semi-permeable membranes for separation processes or apparatus characterised by their form, structure or properties; Manufacturing processes specially adapted therefor
- B01D69/04—Tubular membranes
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D69/00—Semi-permeable membranes for separation processes or apparatus characterised by their form, structure or properties; Manufacturing processes specially adapted therefor
- B01D69/06—Flat membranes
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D71/00—Semi-permeable membranes for separation processes or apparatus characterised by the material; Manufacturing processes specially adapted therefor
- B01D71/06—Organic material
- B01D71/66—Polymers having sulfur in the main chain, with or without nitrogen, oxygen or carbon only
- B01D71/68—Polysulfones; Polyethersulfones
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J5/00—Manufacture of articles or shaped materials containing macromolecular substances
- C08J5/18—Manufacture of films or sheets
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J5/00—Manufacture of articles or shaped materials containing macromolecular substances
- C08J5/20—Manufacture of shaped structures of ion-exchange resins
- C08J5/22—Films, membranes or diaphragms
- C08J5/2206—Films, membranes or diaphragms based on organic and/or inorganic macromolecular compounds
- C08J5/2218—Synthetic macromolecular compounds
- C08J5/2256—Synthetic macromolecular compounds based on macromolecular compounds obtained by reactions other than those involving carbon-to-carbon bonds, e.g. obtained by polycondensation
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J2381/00—Characterised by the use of macromolecular compounds obtained by reactions forming in the main chain of the macromolecule a linkage containing sulfur with or without nitrogen, oxygen, or carbon only; Polysulfones; Derivatives of such polymers
- C08J2381/06—Polysulfones; Polyethersulfones
Landscapes
- Chemical & Material Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Engineering & Computer Science (AREA)
- Manufacturing & Machinery (AREA)
- Materials Engineering (AREA)
- Dispersion Chemistry (AREA)
- Health & Medical Sciences (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Organic Chemistry (AREA)
- Inorganic Chemistry (AREA)
- Compositions Of Macromolecular Compounds (AREA)
- Manufacture Of Macromolecular Shaped Articles (AREA)
Abstract
The invention pertains to a method for manufacturing a sulfone polymer membrane comprising the steps of: (i) preparing a sulfone polymer solution [solution (SP)] comprising: - at least one sulfone polymer [polymer (P)]; a solvent mixture [mixture (M)] comprising: at least one solvent selected from the group consisting of diesters of formula (Ide) and ester-amide of formula (lea), and optionally comprising at least one diamide of formula (Ida): R1-OOC-Ade-COO-R2 (lde); R1-OOC-Aea-CO-NR3R4 (lea); R5R6N-OC-Ada-CO-NR5R6 (lda), wherein: R1 and R2, equal to or different from each other, are independently selected from the group consisting of C1-C20 hydrocarbon groups; R3, R4, R5 and R6 equal to or different from each other and at each occurrence, are independently selected from the group consisting of hydrogen, C1-C36 hydrocarbon groups, possibly substituted, being understood that R3 and R4 might be part of a cyclic moiety including the nitrogen atom to which they are bound, said cyclic moiety being possibly substituted and/or possibly comprising one or more than one additional heteroatom, and mixtures thereof; Ade, Aea, and Ada equal to or different from each other, are independently a linear or branched divalent alkylene group, and optionally dimethylsulfoxide (DMSO); (ii) processing said solution (SP) into a film; (iii) immersing said film in a non-solvent bath.
Description
The cross reference of related application
This application claims the right of priority of the European application EP 12306621.9 submitted on December 19th, 2012, the full content for all object this application is combined in this by reference.
Technical field
The present invention relates to a kind of method for the manufacture of sulfone polymer film.Particularly, the present invention relates to a kind of method comprising some sulfone polymer solution of use.
Background technology
There is the aromatic series sulfone of sulfobenzide group as the part of their backbone repeat unit of contraposition connection, be an analog thermoplastic polymkeric substance, it is characterized in that high glass-transition temperature, good physical strength and rigidity and outstanding thermotolerance and scale resistance.By means of its machinery, heat and other make us the performance of wishing, these polymkeric substance enjoy more and more broader and diversified commercial applications scope, comprise the coating for widely using field and film significantly.
Manufacturing technology for industrial film is usually included in prepares sulfone polymer solution in a suitable solvent.According to these technology, a kind of transparent polymers soln is precipitated as two phases: i.e. a kind of phase forming the solid-state rich in polymers of membrane matrix, and a kind of phase forming the poor polymkeric substance of the liquid state of fenestra.Polymkeric substance precipitates and can realize in some modes from solution, such as cools, solvent evaporates, by being immersed in the water precipitation or planar water from gas phase.If precipitation rapidly, then to trend towards film that is less and that formed asymmetric significantly for pore-forming drop.If precipitation slowly, then pore-forming drop trends towards poly-attached and curtain coating liquid still for liquid, makes that final hole is relatively large like this and membrane structure is more symmetrical.
In these techniques, but provide stable and uniform polymers soln remains crucial as parent material.
Most aromatic series sulfuryl polymkeric substance can be soluble in some high polar solvent with some chlorinated solvent to form stable solution.These potent solvents comprise N-Methyl pyrrolidone (NMP), N,N-dimethylacetamide (DMAc), pyridine and aniline, vinyl trichloride and sym.-tetrachloroethane.
Pyridine, aniline and chlorinated solvent are more undesirable, because their potential harmful healthy effects.
About NMP and DMAc, they for many years in the manufacture of polysulfones asymmetric membrane for based on being the solvent selected in industry in the hollow fiber spinning method of solution always, these solvents face environment and safety problem now, consider the security risk relevant to its process and possible leakage/discharge in the environment, so explore alternative scheme.
Such as, NMP is notably sorted in hazard class Repr.1B code H360D (may damage unborn baby), eye irritation 2 code H319, STOT SE 3 code H335, skin irritation 2H315 and it is classified as Reprotoxic Cat2 code R61, Xi code R36/37/38 according to European instruction 67/548/EEC according to European directive (EC) numbering 1272/2008.In addition, it is submitted to toxic substance emission inventories (Toxic Release Inventory) (SARA title III the 313rd part).
Similarly, DMAc N, N-N,N-DIMETHYLACETAMIDE by the numbering 1272/2008 of regulation (EC) at annex VI, 3rd part, the index number 616-011-00-4 in table 3.1 (Hazardous substances homogeneous classification and tag inventory) is contained for genotoxicity classification 1B (H360D: " may damage unborn baby ").At the annex VI of regulation (EC) numbering 1272/2008,3rd part, the corresponding classification table 3.2 (the objectionable impurities homogeneous classification from annex I to instruction 67/548/EEC and identity inventory) is genotoxicity classification 2 (R61: " may cause damage to unborn baby ").
This invention therefore provides a kind of for avoiding the solution of environment and the safety problem produced when using NMP, DMAc or other similar solvents and providing a kind of alternative method for the manufacture of film.
Brief Description Of Drawings
Fig. 1 is the amplification picture in the PES film through-thickness cross section from solvent EA
Fig. 2 is the amplification picture in the PES film through-thickness cross section from solvent DE+DMSO
Summary of the invention
Therefore the present invention relates to a kind of method for the manufacture of sulfone polymer film, and the method comprises the following steps:
I () prepares a kind of sulfone polymer solution [solution (SP)] comprising the following:
-at least one sulfone polymer [polymkeric substance (P)];
-a kind of solvent mixture [mixture (M)] comprising the following:
At least one is selected from by having formula (I
de) diester and there is formula (I
ea) the solvent of group of ester-acid amide composition, and optionally comprise at least one there is formula (I
da) diamide:
R
1-OOC-A
de-COO-R
2(I
de)
R
1-OOC-A
ea-CO-NR
3R
4(I
ea)
R
5R
6N-OC-A
da-CO-NR
5R
6(I
da)
Wherein:
-R
1and R
2, be same to each other or different to each other, independently selected from by C
1-C
20the group of alkyl composition;
-R
3, R
4, R
5and R
6, to be same to each other or different to each other and when occurring at every turn, independently selected from lower group, this group is made up of the following: hydrogen, the C that may replace
1-C
36alkyl, should understand R
3and R
4can be a part for the circular part comprising the nitrogen-atoms be bonded thereto, described circular part be possible replace and/or one or more than one extra heteroatoms may be comprised, with and composition thereof;
-A
de, A
eaand A
da, being same to each other or different to each other, is the divalent alkyl of straight or branched independently,
And optionally methyl-sulphoxide (DMSO);
(ii) described solution (SP) is processed as film;
(iii) described film is immersed in non-solvent bath.
The applicant finds, described at least one diester (I
de) and ester-acid amide (I as described in detail above
ea), may with diamide (I
da) and/or DMSO combination, can provide, except there is environmental characteristic positive generally, (not there is environment or toxicity problem), effective solvent mixture in the sulfone polymer solution being suitable for manufacturing film is being provided.
By reference to detailed description of the invention, will be easier to understand and understand this purpose of the present invention and other objects, advantage and feature.
Term " film " uses with its common implication at this, and namely it refers to a kind of discrete, thin generally interface, and the infiltration of the chemical species contacted with it has been controlled at this interface.This interface can be that molecule is uniform, that is, structurally complete and homogeneous (dense film), or it can be chemistry or physically heterogeneous, such as, space containing multiple finite size, hole or hole (porous-film).
Porous-film is characterized by mean pore size and porosity (mark of namely total porous-film) generally.
The film that thickness throughout them has uniform texture is called symmetric membrane generally, it can be fine and close also or porous; The film with the hole of the distribution in uneven thickness throughout them is called asymmetric membrane generally.The feature of asymmetric membrane is thin selective layer (0.1-1 μm thick) and highly porous thick-layer (100-200 μm thick), and this thick-layer plays upholder, and does not almost affect for the stalling characteristic of this film.
Film can be dull and stereotyped form or the form of pipe.Based on their size, tubular film is divided into the tubular film with the diameter being greater than 3mm; There is the capillary membranes of the diameter be included between 0.5mm and 3mm; And there is the tubular fibre of the diameter being less than 0.5mm.Capillary membranes is also often called tubular fibre.
When requiring high flow capacity, flat sheet membrane is generally preferred, and requires in the application of the compact module with high surface area wherein, and tubular fibre is particularly advantageous.
Depend on their application, their mechanical endurance can also be improved film support.The selectivity for film is selected to have the support material of minimum influence.
Solution (SP) comprises the mixture [mixture (M)] of polymkeric substance (P) and solvent.
Term " solvent " is use with its common implication at this, that is, its expression can dissolve another kind of material (solute) to form a kind of material of homodisperse mixture on a molecular scale.When a kind of polymer solute, convention refers to when the mixture generated is transparent and does not have visible to be separated within the system, a kind of polymkeric substance solution in a solvent.The point be separated, is commonly referred to " cloud point ", and be considered to owing to forming polymer agglomerates thing, solution becomes that muddy or fuzzy point.
Mixture (M) is except DMSO and/or diamide (I
da) outside also may comprise, more than one, there is formula (I
de) diester mixture, more than one, there is formula (I
ea) the mixture of ester-acid amide, or one can be comprised or more than a kind of diester (I
de) and a kind of or more than a kind of esteramides (I
ea) mixture.The applicant thinks, not fettered, one or more diester (I by this theory
de) and/or one or more ester-acid amides (I
ea) the purposes of mixture can provide the drying property of improvement for composition.
Mixture (M) comprises one or more than a kind of esteramides (I wherein
ea) embodiment in, esteramides (I should be understood
ea) as described in detail above usually and diamide (I
da) be combined in present mixture (M).
At formula (I
de) and (I
ea) in, R
1and R
2, be same to each other or different to each other, be preferably selected from by C
1-C
20alkyl, C
1-C
20aryl, C
1-C
20alkaryl, C
1-C
20the group of aralkyl group and their mixture composition.
About at formula (I
de) and (I
ae) the middle statement " C used
1-c
20alkyl ", use according to its common implication and it notably contain have from 1 to 20 carbon atom and preferably from 1 or the straight chain of 2 to 10 carbon atoms, ring-type, side chain saturated hydrocarbon chain.
Similarly, " C is stated
1-c
20aryl " to use according to its common implication and it notably contains containing from the aromatic monocyclic of 6 to 12 carbon atoms or polycyclic moiety, preferred monocycle or bicyclic groups, preferred phenyl or naphthyl.
Still, " C is stated
1-c
20aralkyl " to use according to its common implication and it contains saturated alkyl containing one or more than one aromatic monocyclic or the polycyclic moiety alternatively straight chain of base, side chain or ring-type, as benzyl significantly.
Finally, " C is stated
1-c
20alkaryl " to use according to its common implication and it contain containing one or more than one alkyl alternatively the aromatic monocyclic of base or polycyclic moiety as one or more than one have from 1 to 14 carbon atom and preferably from 1 or the straight chain of 2 to 10 carbon atoms, ring-type, side chain saturated hydrocarbon chain.
More preferably at formula (I
de) and (I
ae) in R
1and R
2, be same to each other or different to each other, preferably select free methyl, ethyl, n-propyl, sec.-propyl, normal-butyl, isobutyl-, the tertiary butyl, sec-butyl, 2-Ethyl-butyl, n-pentyl, isopentyl, sec.-amyl sec-pentyl secondary amyl, cyclopentyl, n-hexyl, isohexyl, Sec-Hexyl, 2-ethylhexyl, Zhong Gengji, 3-Methyl-hexyl, 4-Methyl-hexyl, 1-ethyl-pentyl, 2-ethyl-pentyl, 3-ethyl-pentyl, n-octyl, iso-octyl, 3-methyl-heptyl, n-nonyl, positive decyl, n-undecane base, dodecyl, n-tridecane base, n-tetradecane base, Pentadecane base, cyclohexyl, the group of phenyl and benzyl composition.
At formula (I
ea) and (I
da) in, R
3and R
4, R
5and R
6, be same to each other or different to each other and when occurring at every turn, be preferably selected from lower group, this group is made up of the following: C
1-C
20alkyl, C
1-C
20aryl, C
1-C
20alkaryl, C
1-C
20aralkyl, all described groups may comprise one or more than one substituting group, may have one or more than one heteroatoms, and comprise R
3and R
4and the circular part of both the nitrogen-atoms be bonded thereto, described circular part may comprise one or more than one heteroatoms, as Sauerstoffatom or additional nitrogen-atoms.
At formula (I
ea) and (I
da) in, R
3and R
4, R
5and R
6to be same to each other or different to each other and when occurring at every turn, more preferably select the group that free methyl, ethyl, hydroxyethyl, n-propyl, sec.-propyl, normal-butyl, isobutyl-, the tertiary butyl, n-pentyl, isopentyl, hexyl, cyclohexyl form, most preferably select the group that free methyl, ethyl and hydroxyethyl form.
According to the first embodiment of the present invention, formula (I
de), (I
ea) and (I
da) in A, be C
3-C
10the diformazan alkylidene group of side chain.
According to this first embodiment, A is preferably selected from the group of the following composition:
-there is formula MG
a-CH (CH
3)-CH
2-CH
2-or MG
b-CH
2-CH
2-CH (CH
3)-A
mGgroup,
-there is formula ES
a-CH (C
2h
5)-CH
2-or ES
b-CH
2-CH (C
2h
5)-A
eSgroup, and
-their mixture.
In a preferred variant of this first embodiment, mixture (M) also may contain except DMSO:
(i) this diester (I '
de) at least one and at least one diester (I "
de), formula (II may be had with at least one
de) diester combination; Or
(ii) this esteramides (I'
ea) at least one and at least one esteramides (I "
ea), formula (II may be had with at least one
ea) esteramides combination;
(iii) this esteramides (I'
ea) at least one, at least one diamide (I'
da), at least one esteramides (I "
ea) and at least one diamide (I "
da), formula (II may be had with at least one
ea) esteramides and/or at least one there is formula (II
da) diamide combination; Or
(iv) combination of (i) and (ii) and/or (iii),
Wherein:
-(I'
de) be R
1-OOC-A
mG-COO-R
2
-(I'
ea) be R
1-OOC-A
mG-CO-NR
3r
4
-(I'
da) be R
5r
6n-OC-A
mG-CO-NR
5r
6
-(I "
de) be R
1-OOC-A
eS-COO-R
2
-(I "
ea) be R
5r
6n-OC-A
eS-CO-NR
5r
6; And
-(II
de) be R
1-OOC-(CH
2)
4-COO-R
2,
-(II
ea) be R
1-OOC-(CH
2)
4-CO-NR
3r
4,
-(II
da) be R
5r
6n-OC-(CH
2)
4-CO-NR
5r
6,
Wherein:
-A
mGthere is formula MG
a-CH (CH
3)-CH
2-CH
2-or MG
b-CH
2-CH
2-CH (CH
3)-,
-A
eSthere is formula ES
a-CH (C
2h
5)-CH
2-or ES
b-CH
2-CH (C
2h
5)-; And wherein R
1and R
2, be same to each other or different to each other, independently selected from by C
1-C
20alkyl, C
1-C
20aryl, C
1-C
20alkaryl, C
1-C
20the group of aralkyl group composition;
-R
3, R
4, R
5and R
6, be same to each other or different to each other and when occurring at every turn, be selected from by C
1-C
20alkyl, C
1-C
20aryl, C
1-C
20alkaryl, C
1-C
20the group of aralkyl group composition, all described groups may comprise one or more than one substituting group, may have one or more than one heteroatoms, and have and comprise (1) R
3and R
4or R
5and R
6and the circular part of both nitrogen-atoms that (2) are bonded thereto, described circular part may comprise one or more than one heteroatoms, such as Sauerstoffatom or additional nitrogen-atoms.
Above-mentioned formula (I '
de), (I "
de) and (II
de), (I '
ea), (I "
ea) and (II
ea), (I '
da), (I "
da) and (II
da) in, R
1and R
2, preferably methyl, and R
3, R
4, R
5and R
6, be same to each other or different to each other and when occurring at every turn, preferably select the group that free methyl, ethyl, hydroxyethyl form.
In this preferred variant of this embodiment, mixture (M) is preferably made up of any one of (i), (ii), (iii) or (iv) mixture in essence, may combine with DMSO.Other minor components, divided by the gross weight of mixture (M), may preferably occur with the amount being no more than 1%wt, its condition is that they do not change the characteristic of mixture (M) substantially.
According to this variant, mixture (M) may can also comprise the following (or primarily of the following composition) except DMSO:
J () two ester mixture, forms primarily of the following:
-by weight from 70% to 95% have formula (I '
de) diester;
-by weight from 5% to 30% have formula (I "
de) diester, and
-by weight from 0 to 10% as described in detail above there is formula (II
de) diester; Or
(jj) esteramides mixture, forms primarily of the following:
-by weight from 70% to 95% there is formula (I'
ea) esteramides;
-by weight from 5% to 30% have formula (I "
ea) esteramides, and
-by weight from 0 to 10% as described in detail above there is formula (II
ea) any one of esteramides; Or
(jjj) esteramides/bis-ester mixture, forms primarily of the following
-by weight from 70% to 95% there is formula (I'
ea) esteramides and there is formula (I'
da) diamide, wherein (I'
da) representative by weight from 0.01% to 10% (I'
ea) and (I'
da) accumulator weight;
-by weight from 5% to 30% have formula (I "
ea) esteramides and have formula (I "
da) diamide, wherein (I "
da) representative by weight from 0.01% to 10% (I "
ea) and (I "
da) accumulator weight and
-by weight from 0 to 10% as described in detail above there is formula (II
ea) esteramides and diester (II
da) any one; Or
The mixture of (j) as described in detail above and (jj) and/or (jjj).
Wherein A is an example of the useful mixture based on diester of side chain is business-like by Su Wei (Solvay)
iRIS solvent.
iRIS solvent is the mixture of following diester, and this mixture comprises (higher than 80wt.%) ethyl succinic acid dimethyl ester and 2-methylglutaric acid dimethyl ester in essence.
In another embodiment, formula (I
de), (I
ea) and (I
da) in A there is formula (CH
2)
rlinear bivalent alkylidene group, wherein r is the integer from 2 to 4.
In a variant of this embodiment, mixture (M) also may contain except DMSO:
(k) this there is formula (III
4 de) diester, this has formula (III
3 de) diester and this there is formula (III
2 de) diester at least one; Or
(kk) this has formula (III
4 ea) esteramides, this has formula (III
3 ea) esteramides and this there is formula (III
2 ea) esteramides at least one; Or
(kkk) this has formula (III
4 ea) esteramides, this has formula (III
3 ea) esteramides and this there is formula (III
2 ea) esteramides at least one, and this has formula (III
4 da) diamide, this has formula (III
3 da) diamide and this there is formula (III
2 da) diamide at least one; Or
(kv) combination of (k) and (kk) and/or (kkk),
Wherein:
-(III
4 de) be R
1-OOC-(CH
2)
4-COO-R
2
-(III
3 de) be R
1-OOC-(CH
2)
3-COO-R
2
-(III
2 de) be R
1-OOC-(CH
2)
2-COO-R
2
-(III
4 ea) be R
1-OOC-(CH
2)
4-CO-NR
3r
4
-(III
3 ea) be R
1-OOC-(CH
2)
3-CO-NR
3r
4
-(III
2 ea) be R
1-OOC-(CH
2)
2-CO-NR
3r
4
-(III
4 da) be R
5r
6n-OC-(CH
2)
4-CO-NR
5r
6
-(III
3 da) be R
5r
6n-OC-(CH
2)
3-CO-NR
5r
6
-(III
2 da) be R
5r
6n-OC-(CH
2)
2-CO-NR
5r
6
Wherein R
1and R
2, being same to each other or different to each other, is C independently
1-C
20alkyl, C
1-C
20aryl, C
1-C
20alkaryl, C
1-C
20aralkyl group;
-R
3, R
4, R
5and R
6, be same to each other or different to each other and when occurring at every turn, be selected from the group be made up of the following: C
1-C
20alkyl, C
1-C
20aryl, C
1-C
20alkaryl, C
1-C
20aralkyl group, all described groups may comprise one or more than one substituting group, may have one or more than one heteroatoms, and have and comprise (1) R
3and R
4or R
5and R
6and the circular part of both nitrogen-atoms that (2) are bonded thereto, described circular part may comprise one or more than one heteroatoms, such as Sauerstoffatom or additional nitrogen-atoms.
At above-mentioned formula (III
4 de), (III
3 de), (III
2 de), (III
4 ea), (III
3 ea) and (III
2 ea), (III
4 da), (III
3 da) and (III
2 da) in, R
1and R
2preferably methyl, and R
3, R
4, R
5and R
6, be same to each other or different to each other, preferably select the group that free methyl, ethyl and hydroxyethyl form.
According to certain the preferred variant in this embodiment, mixture (M) also can may comprise except DMSO:
L two ester mixtures that () forms primarily of dimethyl adipate (r=4), Methyl glutarate (r=3) and dimethyl succinate (r=2); Or
(ll) primarily of H
3cOOC-(CH
2)
4-CO-N (CH
3)
2, H
3cOOC-(CH
2)
3-CO-N (CH
3)
2and H
3cOOC-(CH
2)
2-CO-N (CH
3)
2the esteramides mixture of composition; Or
(lll) two ester mixtures of diethylene adipate (r=4), ethyl glutarate (r=3) and diethyl succinate (r=2); Or
(lv) primarily of H
5c
2oOC-(CH
2)
4-CO-N (CH
3)
2, H
5c
2oOC-(CH
2)
3-CO-N (CH
3)
2and H
5c
2oOC-(CH
2)
2-CO-N (CH
3)
2the esteramides mixture of composition; Or
The mixture of (v) diisobutyl adipate (r=4), pentanedioic acid diisobutyl ester (r=3) and succinic acid diisobutyl ester (r=2); Or
(vl) primarily of H
9c
4oOC-(CH
2)
4-CO-N (CH
3)
2, H
9c
4oOC-(CH
2)
3-CO-N (CH
3)
2and H
9c
4oOC-(CH
2)
2-CO-N (CH
3)
2the esteramides mixture of composition; Or
(vll) their mixture.
An exemplary embodiment of the variant listed in (l) part is above two ester mixtures, and this mixture forms primarily of the following:
-by weight from 9% to 17% dimethyl adipate;
-by weight from 59% to 67% Methyl glutarate; And
-by weight from 20% to 28% dimethyl succinate.
Wherein A is that an example of the useful mixture based on diester of straight chain is sold by Su Wei (Solvay)
rPDE solvent.
rPDE solvent is the mixture of following diester, and this mixture comprises (higher than 70wt.%) Methyl glutarate and dimethyl succinate in essence.
What can use in the present compositions has formula (I
de) diester, notably can according to EP 1991519A (Rhodia Operations (RHODIA OPERATIONS)) 11/19/2008 teach content preparation.Can in the present compositions may with there is formula (I
da) diamide combinationally use there is formula (I
ea) esteramides, notably can teach content preparation according to WO2011/154661 (Rhodia Operations) 12/15/2011 and WO 20110166025 (Rhodia Operations) 07/07/2011.
Based on the gross weight of mixture (M), mixture (M) comprises at least 10% usually, described one or more diester (I of preferably at least 20%, more preferably at least 30%wt
de) and/or one or more esteramides (I
ea).
When mixture (M) comprises esteramides (I
ea) time, described mixture (M) also will comprise by divided by (I generally
ea) and (I
da) accumulator weight by weight in 0.1% to 10% the diamide (I of amount
da).
According to some embodiment, mixture (M) comprises methyl-sulphoxide (DMSO) and at least one is selected from by having formula (I
de) diester and there is formula (I
ea) esteramides composition solvent.
In these embodiments, there is formula (I
de) and (I
ea) solvent and DMSO between weight ratio, preferably from 1/99 to 99/1, preferably from 20/80 to 80/20, more preferably from 70/30 to 30/70.
The characteristic that those skilled in the art will select suitable weight ratio to regulate mixture (M) in composition of the present invention rightly.
Mixture (M) except DMSO and may have formula (I
de), (I
ea) and (I possibly
da) solvent outside can also comprise the other solvent of at least one.
If used, the amount of described other solvent is usually less than the amount of optional DMSO and has formula (I
de), (I
ea) and possible (I
da) both total amounts of solvent.Still, when described other solvent exists, relative to DMSO and there is formula (I
de), (I
ea) and possible (I
da) the total amount of solvent, the amount of described other solvent be preferably lower than 25%wt, be preferably lower than 20%wt, more preferably lower than 15%wt, so that more preferably lower than 10%wt.
The exemplary embodiment that may be used for the other solvent of mixture (M) in composition of the present invention comprises significantly:
-fat hydrocarbon, these aliphatic hydrocarbons comprise, and more specifically, paraffin is such as, particularly, pentane, hexane, heptane, octane, nonane, decane, undecane, dodecane or hexanaphthene, and naphthalene and aromatic hydrocarbons and more specifically aromatic hydrocarbons is such as, particularly, benzene, toluene, dimethylbenzene, isopropyl benzene, the petroleum cuts be made up of alkyl benzene mixture;
-aliphatics or aromatic halohydrocarbons class, these aliphatics or aromatic halohydrocarbons comprise more specifically, perchlorizing hydro carbons such as, particularly, zellon, hexachloroethane; Partial oxidation hydro carbons such as methylene dichloride, chloroform, 1,2-ethylene dichloride, 1，1，1-trichloroethane, sym.-tetrachloroethane, pentaline, trieline, 1-chlorobutane, 1,2-dichlorobutane; Mono chloro benzene, 1,2-dichlorobenzene, 1,3-dichlorobenzene, Isosorbide-5-Nitrae-dichlorobenzene, the mixture of 1,2,4-trichlorobenzene or different chlorobenzene;
-aliphatics, alicyclic or aromatic ether is oxide-based, more specifically, diethyl oxide, dipropyl oxide compound, diisopropyl oxide, dibutyltin oxide, methyl tertiary butyl ether (methyltertiobutylether), diamyl oxide compound, diisoamyl oxide compound, glycol dimethyl ether, ethylene glycol diethyl ether, ethylene glycol dibutyl ether, benzyl oxide compound; Dioxane, tetrahydrofuran (THF) (THF);
-gylcol ether, such as ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, ethylene glycol ether, ethyleneglycol monopropylether, ethylene glycol monobutyl ether, ethyleneglycol monophenylether, ethylene glycol monobenzyl ether, diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, Diethylene Glycol mono-n-butyl ether;
-glycol ether ester, such as ethylene glycol monomethyl ether acetate, ethylene glycol monoethyl ether acetate, ethylene glycol monomethyl ether acetate;
-ol class, such as methyl alcohol, ethanol, diacetone alcohol;
-one class, such as acetone, methyl ethyl ketone, methyl iso-butyl ketone (MIBK), diisobutyl ketone, pimelinketone, isophorone;
-straight chain or the ester class of ring-type, such as: isopropyl acetate, n-butyl acetate, methyl acetoacetate, dimethyl phthalate, gamma-butyrolactone;
-straight chain or the carboxyl acylamide of ring-type, such as N,N-dimethylacetamide (DMAC), N, N-diethyl acetamide, dimethyl formamide (DMF), diethylformamide or METHYLPYRROLIDONE (NMP);
-organic carbonate class, such as methylcarbonate, diethyl carbonate, dipropyl carbonate, dibutyl carbonate, ethylmethyl carbonate, NSC 11801, vinylene carbonate;
-phosphoric acid ester, such as trimethyl phosphite 99, triethyl phosphate;
-ureas, such as tetramethyl-urea, tetraethyl urea.
Comprise the embodiment of other solvent for wherein mixture (M), mixture (M) is preferably containing the organic solvent (CMR solvent) not being named as carcinogenic, mutagenesis or genotoxicity according to chemical producting safety classification; More properly, mixture (M) is advantageously substantially free of NMP, DMF and DMAC.
But, be substantially devoid of any other solvent that is different from DMSO and containing having formula (I
de), (I
ea), (I
da) the mixture (M) of solvent, namely in essence by having formula (I
de) and (I
ea) and possible DMSO and/or (I
da) the mixture (M) of solvent composition be preferred mixture.
Except having formula (I
de), (I
ea) and possible (I
da) solvent and possible DMSO outside, in mixture (M), also may there is a small amount of impurity, solvent trace and resistates, and these can not affect the characteristic of mixture (M).Based on the gross weight of mixture (M), it is usually tolerable that the total amount of other components described is up to 1%wt.
Preferably, composition of the present invention only comprises a kind of polymkeric substance (P).
For the purposes of the present invention, statement " aromatic series sulfone polymer (P) " is intended to represent any polymkeric substance, and at least 50% mole of its repeating unit comprises at least one and has formula-Ar-SO
2-Ar '-group [repeating unit (R
sP)], wherein Ar and Ar', is same to each other or different to each other, and is aromatic group.
In first preferred embodiment of the present invention, the described repeating unit R of aromatic series sulfone polymer (P)
sPfor repeating unit (R
sP-1), in their imido form (R
sP-1-A) and/or the form [(R of amido acid
sP-1-B) and (R
sP-1-C)]:
Wherein:
→ represent isometry, make the group of these arrow indications in any repeating unit can be as directed or exist in transposition like this;
Ar " be selected from lower group, this group is made up of the following:
With the corresponding optional structure replaced, wherein Y be-O-,-C (O)-,-(CH
2)
n-,-C (CF
3)
2-,-(CF
2)
n-, wherein n is the integer from 1 to 5, and their mixture.
In second preferred embodiment of the present invention, the repeating unit (R of polymkeric substance (P)
sP) be preferably the repeating unit (R meeting following formula
sP-2):
-Ar
1-(T’-Ar
2)
n-O-Ar
3-SO
2-[Ar
4-(T-Ar
2)
n-SO
2]
m-Ar
5-O-(R
SP-2)
Wherein:
-Ar
1, Ar
2, Ar
3, Ar
4and Ar
5, be same to each other or different to each other and when occurring at every turn, be aromatic series monokaryon or multinuclear group independently;
-T and T ', is same to each other or different to each other and when occurring at every turn, is key independently or optionally comprises one or more than one heteroatomic divalent group; Preferably T ' is selected from the group be made up of the following: key ,-CH
2-,-C (O)-,-C (CH
3)
2-,-C (CF
3)
2-,-C (=CCl
2)-,-SO
2-,-C (CH
3) (CH
2cH
2cOOH)-and there is the group of following chemical formula:
and
Preferably T is selected from the group be made up of the following: key ,-CH
2-,-C (O)-,-C (CH
3)
2-,-C (CF
3)
2-,-C (=CCl
2)-,-C (CH
3) (CH
2cH
2cOOH)-and there is the group of following chemical formula:
and
-n and m, is same to each other or different to each other, and is the integer of zero or 1 to 5 independently.
Sulfone polymer in this second preferred embodiment is ether sulfone polymer.
Aromatic series sulfone polymer (SP) according to a second, preferred embodiment of the present invention, comprises at least 50% mole, the repeating unit (R of preferably 70% mole, more preferably 75% mole
sP-2), also more preferably, as described in detail above, it does not comprise except repeating unit (R
sP-2) beyond repeating unit.
According to the repeating unit (R of the polymkeric substance (P) of this preferred embodiment
sP-2), notably can be selected from by those groups formed with chemical formula (S-A) to (S-D) below this:
Wherein:
-each R ', be same to each other or different to each other, select the group that free halogen, alkyl, thiazolinyl, alkynyl, aryl, ether, thioether, carboxylic acid, ester, acid amides, imide, basic metal or alkaline earth metal sulfonate, alkyl sulfonic ester, basic metal or alkaline earth metal phosphonate salt, phosphonate ester, amine and quaternary ammonium form;
-T and T ', is same to each other or different to each other, and is key or optionally comprises one or more than one heteroatomic divalent group; Preferably T ' is selected from the group be made up of the following: key ,-CH
2-,-C (O)-,-C (CH
3)
2-,-C (CF
3)
2-,-C (=CCl
2)-,-C (CH
3) (CH
2cH
2cOOH)-,-SO
2-and there is the group of following chemical formula:
and
Preferably T is selected from the group be made up of the following: key ,-CH
2-,-C (O)-,-C (CH
3)
2-,-C (CF
3)
2-,-C (=CCl
2)-,-C (CH
3) (CH
2cH
2cOOH)-and there is the group of following chemical formula:
and
-j ' be zero or for from 0 to 4 integer.
Aromatic series sulfone polymer (P) typically has advantageously at least 150 DEG C, preferably at least 160 DEG C, more preferably the second-order transition temperature of at least 175 DEG C.
There is the repeating unit (R of formula (S-D)
sP) be preferably selected from the group be made up of following repeating unit:
And their mixture.
As described in detail above, the repeating unit (R of formula (S-C) is met
sP) be preferably selected from by the group formed with lower unit:
And their mixture.
Use its repeating unit for the aromatic series sulfone polymer (SP) of repeating unit (ii) (poly-diphenyl disulfoxide hereinafter), use its repeating unit for the aromatic series sulfone polymer (SP) of repeating unit (j) (Polyphenylene Sulfone hereinafter or PPSU), use its repeating unit for the aromatic series sulfone polymer (SP) of repeating unit (jj) (polyether ethersulfone hereinafter), use the aromatic series sulfone polymer (SP) that its repeating unit is repeating unit (jjj) and optionally other repeating unit (jj) (polyethersulfone hereinafter or PES), use the aromatic series sulfone polymer (SP) that its repeating unit is repeating unit (jv) and optionally other repeating unit (jj) (polysulfones hereinafter or PSF), obtain good result.
Polyphenylene Sulfone (PPSU) is notably from extraordinary Polymer Company (Solvay Specialty Polymers USA, the L.L.C) conduct of U.S. Su Wei
r PPSU is obtainable.Polysulfones (PSF) is notably from the conduct of U.S. Su Wei extraordinary Polymer Company
pSF is obtainable.Polyethersulfone (PES) is notably from the conduct of U.S. Su Wei extraordinary Polymer Company
a PES or conduct
r-PES is obtainable.
Use polyethersulfone (PES), that is, the aromatic series sulfone polymer (SP) using its repeating unit to be repeating unit (jjj) and optional other repeating unit (jj), has obtained very good result.
Sulfone polymer solution [solution (SP)] can be prepared in any conventional manner in step (i).Such as, mixture (M) can be added in polymkeric substance (P), or preferably, polymkeric substance (P) can be added in mixture (M), or even polymkeric substance (P) and mixture (M) can be combined simultaneously.
Advantageously at least 25 DEG C, preferably at least 30 DEG C, more preferably at least 40 DEG C and even prepare solution (SP) at the temperature of preferred at least 50 DEG C.Advantageously be less than 180 DEG C, be preferably less than 170 DEG C, be more preferably less than 160 DEG C and prepare solution (SP) under being even more preferably less than the temperature of 150 DEG C.Certainly, for solution (SP) preparation process (i), higher temperature can be used, however from reality and/or the viewpoint of economy, they are not preferred.
The total concn of this polymkeric substance (P) in solution (SP) is, based on the gross weight of this solution, by weight at least 10%, preferably by weight at least 12%.Typically, based on the gross weight of solution (SP), in solution, the concentration by weight of polymkeric substance (P) is no more than 50%, and preferably this concentration by weight is no more than 40%, and more preferably this concentration by weight is no more than 30%.
Solution (SP) can contain additional component, such as pore former, nucleator, weighting agent and analogue.Suitable pore former such as polyvinylpyrrolidone (PVP) and polyoxyethylene glycol (PEG), wherein PVP is preferred.When with by weight from 0.1% to 5%, preferably by weight from 0.5% to 3% amount add to solution (SP) time, obtain the solution of clear homogeneous.Pore former is removed at least partly usually from the film in the non-solvent bath step (iii) (if not removing completely).
Depend on the viscosity of the solution (SP) in the efficiency of the dissolution rate of component, temperature, mixing device, preparation and similar factor, the mixing time obtained required by solution (SP) can change on a large scale.Any applicable mixing equipment can be used.Preferably, select mixing equipment to reduce the amount being entrained in air in solution (SP), thisly carry the defect that can cause in most telolemma secretly.Can easily in a sealed vessel, optionally keep carrying out under an inert atmosphere mixing of this polymkeric substance (P) and mixture (M).Find that inert atmosphere and nitrogen atmosphere are more precisely particularly advantageous in preparing the solution (SP) comprising PVP.
Usually, the solubleness of polymkeric substance (P) in solvent mixture (M) at the temperature of the solution in step (ii) process of method of the present invention, relative to the gross weight of solution, should be and be greater than 10% by weight, be preferably greater than 12% by weight, be more preferably greater than 15% by weight.
Term " solubleness " is defined as the maximum of the polymkeric substance measured in the mode of the polymer weight in the solution of unit weight at this, this polymkeric substance dissolve at a given temperature thus provide transparent, uniform solution and there is not any being separated within the system.
In addition, amount required for cloud point is reached (based on the weight of solution (SP) to be usually less than, be less than 40%wt, preferably be less than 25%wt), the limited amount non-solvent being used for polymkeric substance (P) can be added in the solution (SP) obtained in step (i).This non-solvent is by usually identical with the non-solvent used in the step (iii) of the method.Therefore non-solvent will describe in following steps (iii).Do not fettered by this theory, usually should understand the interpolation of a certain amount of non-solvent in solution (SP), the speed of removing mixing/coagulation in step (iii) will be increased in, to provide more favourable film form.
Once prepare uniform and transparent solution (SP), solution (SP) is processed as film.
Term " film " refers to the layer of the solution (SP) that this solution of processing (SP) obtains later as used herein.Depend on the final form of film, when requiring flat sheet membrane, this film can be smooth, or when to obtain tubulose or the tunica fibrosa of hollow time, this film is tubulose in shape.
Carry out step (ii) period solution temperature can with or can not with solution preparation step (i) period temperature identical.Typically be no more than 180 DEG C at the solution temperature carrying out step (ii) period, preferably it is no more than 170 DEG C, and more preferably it is no more than 160 DEG C, and even more preferably it is no more than 150 DEG C.
For the solution (SP) in procedure of processing (ii) period, the lower boundary of processing temperature is not crucial, and its condition is that solution (SP) still maintains sufficient solubleness and viscosity characteristics.Room temperature can be used significantly.
At the temperature of procedure of processing (ii), the viscosity of solution (SP) typically is at least 1Pa.s.The viscosity of the solution (SP) in described condition is typically no more than 100Pa.s.
Be processed as film for by solution (SP), can use routine techniques, it is preferred for should understanding casting technology.
Depend on the final form of the film manufactured, use different casting technology.When the finished product are smooth films, by casting knife or line rod (draw-down bar), this polymers soln is cast into the film on smooth upholder, and this upholder is plate, band or fabric or another kind of micro-supporting film typically.
Thus, in the first embodiment of the present invention, method of the present invention comprise by this solution (SP) on the support curtain coating become the step (ii) of smooth film.
Tubular fibre and capillary membranes can be obtained by so-called wet spinning processes.In a kind of so method, generally solution (SP) is pumped across spinneret, this spinneret is the ring nozzle comprising at least two Concentric capillary tubings: the first external capillary passed through for solution (SP), and for supporting the second internal capillaries that fluid (being commonly referred to as " stream (lumen) ") passes through.This stream plays the effect of the upholder for casting solutions (SP), and keeps the hole of the precursor of this tubular fibre or kapillary open.This stream can be gas under the spinning condition of fiber, or preferably, is liquid.The selection of this stream and its temperature depend on most feature required by telolemma, because they may have significant impact for the size in the hole in this film and distribution.In general, this stream is not strong non-solvent for this polymkeric substance (P), or alternately, and it contains solvent for this polymkeric substance (P) or Weak solvent.This stream typically with for the non-solvent of this polymkeric substance (P) and solvent miscible.The temperature of this stream is generally close to the temperature of this solution (SP).
In the exit of this spinneret, in atmosphere or in controlled atmosphere after one brief stay period, by this tubular fibre or the precursor of kapillary be immersed in this non-solvent bath, wherein there is precipitation thus form tubular fibre or capillary membranes in this polymkeric substance.
Thus in the second embodiment of the present invention, method of the present invention comprises the step (ii) this polymers soln curtain coating being become the tubular film around support fluid.
The curtain coating of this polymers soln has been come typically by spinneret.This support fluid forms the hole of this tubular fibre or capillary membranes.When this support fluid is liquid, this fiber precursor is immersed non-solvent bath and also advantageously eliminates support fluid from the inside of this fiber.
Tubular film is comparatively large due to their diameter, uses and produces with the method diverse ways used for the production of hollow-fibre membrane.
In the third embodiment of the present invention, method of the present invention comprises the step (ii) this polymers soln curtain coating being become the tubular film on support tubular material.
After the processing of solution (SP) has completed to obtain film, with any one form as previously discussed, described film is immersed in the non-solvent bath in step (iii).For the precipitation from directs polymer (P) in solution (SP), this step is effective generally.This polymkeric substance be settled out (P) has therefore advantageously generated final membrane structure.
As used herein, be used to refer to can not a kind of material of given component of solvent soln or mixture for term " non-solvent ".
The non-solvent be applicable to of polymkeric substance (P) is water and fatty alcohol, preferably has the fatty alcohol of short chain (such as from 1 to 6 carbon atom), is more preferably methyl alcohol, ethanol and Virahol.The blend of described preferred non-solvent can be used, namely comprise the blend of water and one or more fatty alcohol.Preferably, the non-solvent of non-solvent bath selects the group that free water, fatty alcohol defined above and their mixture form.In addition, non-solvent bath except non-solvent (such as, as described in detail above, in addition to water, except fatty alcohol or dewater and fatty alcohol mixture except) also can comprise a small amount of (typically, relative to non-solvent bath gross weight, be up to 40%wt, be as general as 25%wt to 40%wt) the solvent for polymkeric substance (P).Solvent/non-solvent mixture is used advantageously to allow the porosity controlling this film.Non-solvent be usually selected from for the preparation of the mixture (M) of solution (SP) miscible those.Preferably, non-solvent is in the method for the invention water.Water is the most cheap non-solvent and it can use in a large number.Mixture (M) advantageously miscible in and in water soluble, this is the extra advantage of of method of the present invention.
Non-solvent in settling bath remains at least 0 DEG C, the temperature of preferably at least 15 DEG C, more preferably at least 20 DEG C usually.Non-solvent in settling bath usually remain on be less than 90 DEG C, be preferably less than 70 DEG C, be more preferably less than the temperature of 60 DEG C.
Thermograde between this cast film and non-solvent bath can affect pore size in final film and/or pore distribution, because it affects the speed that polymkeric substance (P) precipitates from solution (SP).If precipitation rapidly, so generally form one deck skin by the surface contacted with this non-solvent at this cast film, this by the diffusion of non-solvent in this polymers soln body of typically slowing down, thus causes the film with unsymmetrical structure.If slowly, the pore-forming drop (being formed when contacting with this non-solvent) of so rich solvent-laden liquid phase tends to agglomeration to precipitation usually, and this polymers soln is still fluid.Consequently, this film will have evenly, symmetrical structure.The suitable temperature of this non-solvent bath can be determined for often kind of particular case with the experiment of routine.
Once remove from this settling bath, this film can stand extra process, such as, rinse.As last step, this film is typically dried.
The invention still further relates to the film obtained by method as described above.
The film obtained from method of the present invention is preferably porous-film.Typically, this film has unsymmetrical structure.The scope of the porosity of this film can be from 3% to 90%, preferably from 5% to 80%.
This some holes can have the mean diameter of at least 0.001 μm, at least 0.005 μm, at least 0.01 μm, at least 0.1 μm, at least 1 μm, at least 10 μm and at least 50 μm.Such as, in " Liv Ullmann industrial chemistry encyclopaedia (the Ullmann's Encyclopedia of Industrial Chemistry) " the 7th edition that publish in John Wiley and Sons company limited H.Strathmann " film and membrane separation process (Membranes and Membrane Separation Processes) " (DOI:10.1002/14356007.a16_187.pub2) in describe suitable technology for measuring the mean pore size in porous-film.
Be combined in this patent, patent application and the disclosure content of publication and the afoul degree of the description of the application by reference if any to term may be caused unclear, then this explanation should be preferential.
Describe the present invention in more detail referring now to following instance, the object of these examples is only illustrative and is not intended to limit the scope of the invention.
Raw material
-ester-acid amides (EA) is that one comprises and has formula MeO-C (O)-CH (Me)-CH
2cH
2c (O)-NMe
2with MeO-C (O)-CH (the Et)-CH of small number
2-C (O)-NMe
2me possibly
2n-C (O)-CH (Me)-CH
2cH
2c (O)-NMe
2and/or Me
2n-C (O)-CH (Et)-CH
2-C (O)-NMe
2the mixture of ester-acid amide, wherein Me=methyl, this esteramides (EA) is at trade(brand)name POLAR CLEAN from Su Wei
(R)lower commercially available;
-diester (DE) is the mixture be made up of ethyl succinic acid dimethyl ester and 2-methylglutaric acid dimethyl ester a kind of main (being greater than 80wt%), and this diester (DE) is in trade(brand)name from Su Wei
commercially available under IRIS;
-PES is
pES 3000MP, from the commercially available a kind of polyether sulfone polymer of the extraordinary Polymer Company of U.S. Su Wei;
-PSU is in trade(brand)name from the extraordinary Polymer Company of U.S. Su Wei
lower commercially available a kind of polysulfone polymer;
-PVP is a kind of polyvinyl pyrrolidone polymers.
Preliminary investigation for solubleness:
Initial solubility studies is the solubleness in order to assess PES and PSU, and mixing with DMSO in the mixture of (50/50wt/wt) in ester-acid amide (EA) and at diester (DE) as described in detail above is as described in detail above carried out.
Find that at room temperature PES is dissolved in these two kinds of solvent mixtures with 10%wt.
Find when being heated to about 120 DEG C, PSU is dissolved in two kinds of solvent mixtures with 10%wt.At least for ester-acid amide (EA) solvent mixture, at room temperature keep solubleness.
Because this solubleness behavior, find that two kinds of solvent mixtures are suitable for manufacturing the solution being applicable to processing further under the form of film.
For the manufacture of the universal program of the sulfone polymer solution manufactured for film.
In the mixing tank being equipped with deflocculate blade, by degassed for solvent EA and at 80 DEG C heat; Once reach this temperature, first PVP introduced and stir 20-30min with 500rpm.Then, add PES, keep stirring with 500rpm during adding, and then to continue at 80 DEG C and to stir 40 to 60 minutes at 200 rpm.Obtain the clear solution of PVP of PES and 5%wt containing 16% or 20%wt.After the storage of 3 days, by homogeneous solution stability at room temperature described in visualize: do not observe and be separated or crystallization.
Find the viscosity of solution that so obtains at room temperature (25 DEG C) be less than 100Pa x sec, and to remain unchanged after the storage of 3 days.
As described above about the result of the preparation of this solution, clearly illustrate that, the fitness of solution as described in detail above in storage power and in viscosity, is advantageously used in the film obtained by conventional liq processing technology.In addition, the miscible property of the solvent used is particularly conducive to the effective coagulation obtained in the non-solvent bath of routine, to ensure the film obtaining having suitable construction.
Similarly, mix the PVP solution of PES and 5%wt preparing 20%wt in the mixture of (50/50wt/wt) with DMSO at diester (DE) as described in detail above.
The program of coagulation film for cast film and in non-solvent bath
In order to obtain film, by the solution of PES and PVP obtained in both mixtures of solution E A and DE and DMSO as described in detail above, casting knife is used to process on carrier foil.The membranes submerged so obtained removes PVP substantially with this polymkeric substance of coagulation in a water bath.Obtain having the porous-film of about 100 μm of thickness; Microphotograph (magnification=1:500) display in Fig. 1 (film from solvent EA) and Fig. 2 (film from solvent DE+DMSO) respectively in the cross section of its through-thickness.
Claims (15)
1., for the manufacture of a method for sulfone polymer film, comprise the following steps:
I () preparation comprises the sulfone polymer solution [solution (SP)] of the following:
-at least one sulfone polymer [polymkeric substance (P)];
-comprise the solvent mixture [mixture (M)] of the following:
At least one is selected from by having formula (I
de) diester and there is formula (I
ea) the solvent of group of ester-acid amide composition, and optionally comprise at least one there is formula (I
da) diamide:
R
1-OOC-A
de-COO-R
2(I
de)
R
1-OOC-A
ea-CO-NR
3R
4(I
ea)
R
5R
6N-OC-A
da-CO-NR
5R
6(I
da)
Wherein:
-R
1and R
2, be same to each other or different to each other, independently selected from by C
1-C
20the group of alkyl composition;
-R
3, R
4, R
5and R
6, to be same to each other or different to each other and when occurring at every turn, independently selected from lower group, this group is made up of the following: hydrogen, the C that may replace
1-C
36alkyl, should understand R
3and R
4can be a part for the circular part comprising the nitrogen-atoms be bonded thereto, described circular part be possible replace and/or one or more than one extra heteroatoms may be comprised, with and composition thereof;
-A
de, A
eaand A
da, being same to each other or different to each other, is the divalent alkylene groups of straight or branched independently,
And optionally methyl-sulphoxide (DMSO);
(ii) described solution (SP) is processed as film;
(iii) described film is immersed in non-solvent bath.
2. the method for claim 1, wherein this mixture (M) also may comprise except DMSO:
(i) this diester (I '
de) at least one and at least one diester (I "
de), formula (II may be had with at least one
de) diester combination; Or
(ii) this esteramides (I'
ea) at least one and at least one esteramides (I "
ea), formula (II may be had with at least one
ea) esteramides combination;
(iii) this esteramides (I'
ea) at least one, at least one diamide (I'
da), at least one esteramides (I "
ea) and at least one diamide (I "
da), formula (II may be had with at least one
ea) esteramides and/or at least one there is formula (II
da) diamide combination; Or
(iv) combination of (i) and (ii) and/or (iii),
Wherein:
-(I'
de) be R
1-OOC-A
mG-COO-R
2
-(I'
ea) be R
1-OOC-A
mG-CO-NR
3r
4
-(I'
da) be R
5r
6n-OC-A
mG-CO-NR
5r
6
-(I "
de) be R
1-OOC-A
eS-COO-R
2
-(I "
ea) be R
5r
6n-OC-A
eS-CO-NR
5r
6; And
-(II
de) be R
1-OOC-(CH
2)
4-COO-R
2,
-(II
ea) be R
1-OOC-(CH
2)
4-CO-NR
3r
4,
-(II
da) be R
5r
6n-OC-(CH
2)
4-CO-NR
5r
6,
Wherein:
-A
mGthere is formula MG
a-CH (CH
3)-CH
2-CH
2-or MG
b-CH
2-CH
2-CH (CH
3)-,
-A
eSthere is formula ES
a-CH (C
2h
5)-CH
2-or ES
b-CH
2-CH (C
2h
5)-; And wherein R
1and R
2, be same to each other or different to each other, independently selected from by C
1-C
20alkyl, C
1-C
20aryl, C
1-C
20alkaryl, C
1-C
20the group of aralkyl group composition;
-R
3, R
4, R
5and R
6, be same to each other or different to each other and when occurring at every turn, be selected from by C
1-C
20alkyl, C
1-C
20aryl, C
1-C
20alkaryl, C
1-C
20the group of aralkyl group composition, all described groups may comprise one or more than one substituting group, may have one or more than one heteroatoms, and have and comprise (1) R
3and R
4or R
5and R
6and the circular part of both nitrogen-atoms that (2) are bonded thereto, described circular part may comprise one or more than one heteroatoms, such as Sauerstoffatom or additional nitrogen-atoms.
3. the method for claim 1, wherein this mixture (M) also may comprise except DMSO:
(k) this there is formula (III
4 de) diester, this has formula (III
3 de) diester and this there is formula (III
2 de) diester at least one; Or
(kk) this has formula (III
4 ea) esteramides, this has formula (III
3 ea) esteramides and this there is formula (III
2 ea) esteramides at least one; Or
(kkk) this has formula (III
4 ea) esteramides, this has formula (III
3 ea) esteramides and this there is formula (III
2 ea) esteramides at least one, and this has formula (III
4 da) diamide, this has formula (III
3 da) diamide and this there is formula (III
2 da) diamide at least one; Or
(kv) combination of (k) and (kk) and/or (kkk),
Wherein:
-(III
4 de) be R
1-OOC-(CH
2)
4-COO-R
2
-(III
3 de) be R
1-OOC-(CH
2)
3-COO-R
2
-(III
2 de) be R
1-OOC-(CH
2)
2-COO-R
2
-(III
4 ea) be R
1-OOC-(CH
2)
4-CO-NR
3r
4
-(III
3 ea) be R
1-OOC-(CH
2)
3-CO-NR
3r
4
-(III
2 ea) be R
1-OOC-(CH
2)
2-CO-NR
3r
4
-(III
4 da) be R
5r
6n-OC-(CH
2)
4-CO-NR
5r
6
-(III
3 da) be R
5r
6n-OC-(CH
2)
3-CO-NR
5r
6
-(III
2 da) be R
5r
6n-OC-(CH
2)
2-CO-NR
5r
6
Wherein R
1and R
2, being same to each other or different to each other, is C independently
1-C
20alkyl, C
1-C
20aryl, C
1-C
20alkaryl, C
1-C
20aralkyl group;
-R
3, R
4, R
5and R
6, be same to each other or different to each other and when occurring at every turn, be selected from the group be made up of the following: C
1-C
20alkyl, C
1-C
20aryl, C
1-C
20alkaryl, C
1-C
20aralkyl group, all described groups may comprise one or more than one substituting group, may have one or more than one heteroatoms, and have and comprise (1) R
3and R
4or R
5and R
6and the circular part of both nitrogen-atoms that (2) are bonded thereto, described circular part may comprise one or more than one heteroatoms, such as Sauerstoffatom or additional nitrogen-atoms.
4. as method in any one of the preceding claims wherein, wherein mixture (M) be substantially devoid of be different from DMSO any other solvent and this mixture (M) containing having formula (I
de), (I
ea), (I
da) solvent, namely in essence by having formula (I
de) and (I
ea) and possible DMSO and/or (I
da) solvent composition.
5. the method according to any one of Claims 1-4, at least 50% mole of the repeating unit of wherein said polymkeric substance (P) comprises at least one and has formula-Ar-SO
2-Ar '-group [repeating unit (R
sP)], wherein Ar and Ar', is same to each other or different to each other, and is aromatic group, preferably wherein said repeating unit (R
sP) for meeting formula-Ar
1-(T '-Ar
2)
n-O-Ar
3-SO
2-[Ar
4-(T-Ar
2)
n-SO
2]
m-Ar
5-O-(R
sP-2) repeating unit (R
sP-2)
Wherein:
-Ar
1, Ar
2, Ar
3, Ar
4and Ar
5, be same to each other or different to each other and when occurring at every turn, be aromatic series monokaryon or multinuclear group independently;
-T and T ', is same to each other or different to each other and when occurring at every turn, is key independently or optionally comprises one or more than one heteroatomic divalent group; Preferably T ' is selected from the group be made up of the following: key ,-CH
2-,-C (O)-,-C (CH
3)
2-,-C (CF
3)
2-,-C (=CCl
2)-,-SO
2-,-C (CH
3) (CH
2cH
2cOOH)-and there is the group of following chemical formula:
and
Preferably T is selected from the group be made up of the following: key ,-CH
2-,-C (O)-,-C (CH
3)
2-,-C (CF
3)
2-,-C (=CCl
2)-,-C (CH
3) (CH
2cH
2cOOH)-and there is the group of following chemical formula:
and
-n and m, is same to each other or different to each other, and is the integer of zero or 1 to 5 independently.
6. method, the wherein repeating unit (R of this polymkeric substance (P) as claimed in claim 5
sP-2) be selected from the following group be made up of those repeating units with formula (S-A) to (S-D):
Wherein:
-each R ', be same to each other or different to each other, select the group that free halogen, alkyl, thiazolinyl, alkynyl, aryl, ether, thioether, carboxylic acid, ester, acid amides, imide, basic metal or alkaline earth metal sulfonate, alkyl sulfonic ester, basic metal or alkaline earth metal phosphonate salt, phosphonate ester, amine and quaternary ammonium form;
-T and T ', is same to each other or different to each other, and is key or optionally comprises one or more than one heteroatomic divalent group; Preferably T ' is selected from the group be made up of the following: key ,-CH
2-,-C (O)-,-C (CH
3)
2-,-C (CF
3)
2-,-C (=CCl
2)-,-C (CH
3) (CH
2cH
2cOOH)-,-SO
2-and there is the group of following chemical formula:
and
Preferably T is selected from the group be made up of the following: key ,-CH
2-,-C (O)-,-C (CH
3)
2-,-C (CF
3)
2-,-C (=CCl
2)-,-C (CH
3) (CH
2cH
2cOOH)-and there is the group of following chemical formula:
and
-j ' be zero or for from 0 to 4 integer.
7. method, the wherein repeating unit (R of this polymkeric substance (P) as claimed in claim 6
sP-2) for have formula (S-C), be selected from by the repeating unit of the group formed with lower unit:
And their mixture.
8. the method according to any one of claim 1 to 7, wherein the total concn of this polymkeric substance (P) in this solution (SP) is, based on the gross weight of this solution (SP), by weight at least 10%, preferably by weight at least 12%.
9. the method according to any one of claim 1 to 8, wherein this solution (SP) is containing the pore former being selected from the group be made up of polyvinylpyrrolidone (PVP) and polyoxyethylene glycol (PEG).
10. as claimed in any one of claims 1-9 wherein method, described method comprise by this solution (SP) on the support curtain coating become the step (ii) of smooth film.
11. methods as claimed in any one of claims 1-9 wherein, described method comprises the step (ii) this polymers soln curtain coating being become the tubular film around support fluid.
12. methods as claimed in any one of claims 1-9 wherein, described method comprises the step (ii) this polymers soln curtain coating being become the tubular film on support tubular material.
13. methods according to any one of claim 1 to 13, the non-solvent wherein in step (iii) in this non-solvent bath is selected from lower group, and this group is made up of the following:
-water,
-fatty alcohol, preferably has short chain such as from the fatty alcohol of 1 to 6 carbon atom, more preferably methyl alcohol, ethanol and Virahol, and
-their mixture.
14. methods as claimed in claim 13, wherein, relative to the gross weight of this non-solvent bath, this non-solvent bath is extraly containing the solvent for this polymkeric substance (P) of amount being up to 40%wt.
15. 1 kinds of films obtained by the method such as according to any one of claim 1 to 14.
Applications Claiming Priority (3)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| EP12306621 | 2012-12-19 | ||
| EP12306621.9 | 2012-12-19 | ||
| PCT/EP2013/077194 WO2014096071A1 (en) | 2012-12-19 | 2013-12-18 | Method for manufacturing sulfone polymer membrane |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN104918985A true CN104918985A (en) | 2015-09-16 |
| CN104918985B CN104918985B (en) | 2019-08-09 |
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| CN201380071063.XA Expired - Fee Related CN104918985B (en) | 2012-12-19 | 2013-12-18 | Method for manufacturing sulfone polymer film |
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| Country | Link |
|---|---|
| US (1) | US20150352502A1 (en) |
| EP (1) | EP2935420B1 (en) |
| JP (1) | JP6309537B2 (en) |
| CN (1) | CN104918985B (en) |
| WO (1) | WO2014096071A1 (en) |
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| FR3040995B1 (en) | 2015-09-15 | 2019-12-27 | Arkema France | USE OF COMPOUNDS COMPRISING A SULFOXIDE OR SULFONE FUNCTION AND AN AMIDE FUNCTION AS SOLVENTS AND NOVEL SOLVENTS |
| FR3041357B1 (en) * | 2015-09-17 | 2017-09-01 | Rhodia Operations | DETACHING SOLVENTS OF PHOTOSENSITIVE RESINS |
| US11001673B2 (en) | 2016-05-26 | 2021-05-11 | University Of Florida Research Foundation, Incorporated | Aliphatic polysulfones with improved mechanical integrity |
| WO2017205713A1 (en) * | 2016-05-26 | 2017-11-30 | University Of Florida Research Foundation, Inc. | Aliphatic polysulfones with improved mechanical integrity |
| EP3681620A1 (en) * | 2017-09-11 | 2020-07-22 | Solvay Specialty Polymers USA, LLC | Purification methods comprising the use of membranes obtained from bio-based sulfone polymers |
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| FR2961205B1 (en) | 2010-06-09 | 2012-06-29 | Rhodia Operations | PROCESS FOR THE PREPARATION OF ESTERAMIDE COMPOUNDS |
| WO2012079231A1 (en) * | 2010-12-15 | 2012-06-21 | Rhodia (China) Co., Ltd. | Fluoropolymer compositions |
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2013
- 2013-12-18 US US14/654,026 patent/US20150352502A1/en not_active Abandoned
- 2013-12-18 WO PCT/EP2013/077194 patent/WO2014096071A1/en active Application Filing
- 2013-12-18 JP JP2015548500A patent/JP6309537B2/en not_active Expired - Fee Related
- 2013-12-18 EP EP13818727.3A patent/EP2935420B1/en not_active Not-in-force
- 2013-12-18 CN CN201380071063.XA patent/CN104918985B/en not_active Expired - Fee Related
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| US4208508A (en) * | 1977-07-08 | 1980-06-17 | Asahi Kasei Kogyo Kabushiki Kaisha | Semipermeable membranes of polyaryl ether sulfones |
| CN1127996A (en) * | 1994-03-04 | 1996-07-31 | 美国梅姆特克公司 | Large pore synthetic polymer membranes |
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Also Published As
| Publication number | Publication date |
|---|---|
| WO2014096071A1 (en) | 2014-06-26 |
| CN104918985B (en) | 2019-08-09 |
| EP2935420B1 (en) | 2018-05-16 |
| US20150352502A1 (en) | 2015-12-10 |
| EP2935420A1 (en) | 2015-10-28 |
| JP2016500404A (en) | 2016-01-12 |
| JP6309537B2 (en) | 2018-04-11 |
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